Anthraquinoid dyestuffs

ABSTRACT

An anthraquinoid dyestuff which comprises at least one residue of an anthraquinoid disperse dyestuff and at least one residue of a disperse dyestuff of the styryl series.

United States Patent 1 Peter et al.

[4 1 Sept. 18,1973

ANTHRAQUINOID DYESTUFFS Inventors: Richard Peter; Hans-Joerg Angliker;

Angelo Della Casa, all of Basel, Switzerland Assignee: Ciha-Geigy AG, Basel, Switzerland Filed: Nov. 16, 1971 Appl. No.: 199,345

Related U.S. Application Data Continuation-in-part of Ser. No. 843,834, July 22, 1969, Pat. No. 3,663,557.

Foreign Application Priority Data July 26, 1968 Switzerland 11234/68 U.S. Cl 260/376, 260/371, 260/372, 260/373, 260/377, 260/378, 260/380, 260/381 [51] Int. Cl. C09b 1/32, C09b 1/50 [58] Field of Search 260/372, 376, 377

References Cited UNITED STATES PATENTS 2/l97l Neeff 260/377 Primary Examiner-Lorraine A. Weinberger Assistant ExaminerE. Jane Skelly Attorney-Harry Goldsmith et al.

[ 57] ABSTRACT 5 Claims, No Drawings 'mula ample CO-N-(alkyl)-alkylene or -CO-O-aikylene residue, in

ANTHRAQUINOID DYESTUFFS CROSS-REFERENCE TO RELATED APPLICATION This application is a continuation-in-part of application Ser. No. 843,834, filed July 22, 1969, now U.S. 5 Pat, No. 3,663,557.

The present invention provides dyestuffs, which are preferably free from sulphonic acid groups and in which the residue of an anthraqtiinoid dyestuff is linked with a residue of a styryl dyestuff.

The residue of the styryl dyestuff may be either a negative group linked with the double bond of the styryl v grouping, for example, a sulphonamide group of a carboxyl ester group, linked with the residue of the anthraquinoid dyestuff; or, preferably, it is linked through an alkyl group, which is attached to the nitrogen atom in the paraposition of the styryl residue and which may contain any desired substituents. Accordingly, preferred anthraquinone dyestuffs are those which contain a styryl residue of the formula in which A and ii, have the meaning s given-above,'R,

has the same meaning as R,, and the residues R and R may be identical or different from each other, and X represents a residue bound to the residue of the styryl dyestuff through an -SO,- or CO- bridge, being for exan -SO,-arylene, -SO -'N-(alkyl)-alkylene,

which alkyl and alkylene represent unsubstituted orf substituted alkyl, aralkyl or cycloalkyl groups having 0 one or two free valences respectively,

The anthraquirioid residues may be anthraquinone residues bound to the styryl dyestuffs l) in the a-position'or ('2) in'th'e fi-position.

'Antliraquinones substituted in a-position contain, for

example, a substituted amino group or aminophenylamino group which carries the residue of a styryl dyestuff.

Anthraquinones substituted in B-position contain in v the linking position,-'for example, a sulphonyloxy or carbonyloxy residue derived from the corresponding anthraquinonesulphonic or -carboxylic acid.

Valuable dyestuffs are those of the formula Him in which V represents a hydroxyl or imino group, R,

represents an unsubstituted or substituted alkyl group or a residue of the formula R represents an unsubstituted or substituted alkylene group, Y represents an -S0-,,- or preferably a -CO- group; i or 2; c and d each represents a hydrogen or chlorine atom or a methyl, ethyl, methoxy or ethoxy group; X represents a carbalkyl group, a carbonamide group, an arylsulphonyl or a cyano group, and B represents a residue of one of the formulae in which Z, is an amino group which may be alkylated, or a hydroxyl group, Z represents an amino group which may be alkylated or,a nitrogroup or a bromine atom, and Z and 2, each represents a nitro or hydroxyl group or an amino group which may be alkylated.

Of special value are, for example, the dyestuffs of the formulae and II I

I H Z3 0 N X Of particularimportan ce is the dycstuff of the formula in which Z is OH, NH, or NHR where R is methyl or ethyl,

Z, is NO,, Br, Nl-l or NHR where R, is methyl or ethyl,

Z and Z are each, independently,

N0 OH, NH, or NHR where R is methyl or ethyl,

V is -O- or -NH-,

R is C,-C -alkylene,

R is unsubstituted C,-C,, alkyl or C,-C alkyl substituted by cyano, chloro, C -C alkoxy, hydroxy, C,-C alkoxycarbonyl, C,-C alkylcarbonyloxy, C C alkylcarbamoyloxy, phenylcarbamyloxy, C C,

alkoxycarbonyloxy, phenyloxycarbonyloxy, cyanoethoxy, phenyl, chloracetoxy, or benzoyloxy,

c and d are each, independently, H, C], CH;,, C l-l OCH OC,I-l phenylthio or phenoxy, and

X is C -C carbalkoxy,

c -C -alkylcarbonamido,

phenylsulfonyl or cyano.

The groups R, and R each represent alkyl groups containing one to four, preferably two to four, carbon atoms, for example, methyl, ethyl, propyl or n-butyl groups which may be substituted-in the usual manner, for example, arylalkyl residues, for example, benzyl or B-phenethyl residues, halogenated alkyl groups, for example, B-chloroethyl, fififi-triflu'oroethyl, B,7-dichloropropyl, B-cyanoethyl, fl-cyano-ethoxyethyl, alkoxyalkyl, for example, B-methoxyethyl, B-ethoxyethyl or 8-methoxy-butyl, glycidyl, hydroxyalkyl, for example, B-hydroxyethyl, [3,y-dihydroxypropyl, nitroalkyl, for example, B-nitroethyl, carbalkoxy, for example B-carbo (methoxy, othoxy or propoxy)-ethyl [in which the terminal alkyl group-maycarry in the w-position cyano, carbalkoxy and acyloxy groups], B- or 'y-carbo(- methoxy or ethoxy)propyl, acylaminoalkyl, for example, B-( acetyl or formyl)-aminoethyl, acyloxyalkyl, for example, B-acetyloxyethyl, fl-propionyloxyethyl, B-butyryloxyalkyl, ,B,y-diacetoxypropyl, 'y-acetylaminopropyl, y-propionylaminopropyl, B-(alkyl or aryl)-sulphonylalkyl, for example, B-methanesulphonylethyl, B-ethanesulphonylethyl, B-(parachlorobenzenesulphonyl)-ethyl, alkylor arylcarbamoyloxyalkyl, for example, fl-methylcarbamyloxyethyl and B-phenylcarbamyloxyethyl,

alkyloxycarbonyl-oxyalkyl, for example, B-(methoxy, ethoxy or isopropoxy)-carbonyloxyethyl, 'y-acetamidopropyl, B-(para-nitrophenoxy)-ethyl, B-(parahydroxyphenoxy)-ethyl, B-(B-acetylethoxycarbonyl)-ethyl, B-[(B-cyano-, hydroxy-, methoxyor acetoxy)- ethoxycarbonyH-ethyl, cyanoalkoxyalkyl, B-carboxyethyl, B-acetylethyl, 'y-aminopropyl, B-diethylaminoethyl, B-cyanoacetoxyethyl and B-benzoylor B-(para-alkoxy or phenoxy-benzoyl-ethoxy groups.

Generally, the group R contains no more than 18 carbon atoms.

The group R, is an alkyl group containing one to four carbon atoms, which may contain one or more substituents, for example, hydroxyl or acyloxy groups.

The present invention also provides a process for preparing the above-mentioned dyestuffs, wherein a reactive anthraquinone derivative is condensed with a reactive styryl dyestuff and, if desired, acylated with a fibrereactive acylating agent.

Preferred reactants are those of which one contains a labile negative group and the other a substitutable nucleo-philic group, for example, a hydroxyl, mercapto or amino group. It is also possible to carry out other reactions on active double bonds.

A. Starting compounds of the styryl series (I) Reactive styryl dyestuffs that contain a labile negative residue, for example the styryl dyestuffs of the formulae NC CIHD NC CHrCHzCl and CIhCHgCl and '(described in Swiss Pat. application Ser. No. 6350/68 Case 6448).

(ll) Reactive styryl dyestuffs that contain a nucleophilic substitutable residue, for example, the dyestuffs of the formulae CZH5 CH NC\ /C=CH N(CHCHOH) NC NC\ z 4CaHa C=CH N\ CHaOO C CHICHQOH CH:

and

/C=CH CHgCHzOH); HsCeOz The styryl dye stuffs can be prepared in the usual manner by way of the Vilsmeyer reaction from a dialkylaniline and condensation of the intermediately formed 'y-formylaniline with a methylene-active compound.

Methylene-active compounds of the formula NC- CH -X suitable for the reaction are, for example:

malonic acid dinitrile,

cyanoacetic acid methyl ester, ethyl ester and butyl ester,

cyanoacetamide,

cyanoaceto dimethylamide and methylamide,

methylsulphonyl acetonitrile,

phenylsulphonylacetonitrile and para-toluylsulphonylacetonitrile. B. Starting compounds of the anthraquinone series (I) Starting compounds that contain a negative group which is labile (i.e. can be eliminated) 1. Anthraquinone compounds that contain a negative mobile substituent in the a-position, for example:

l-halogenanthraquinones, preferably l-bromoor l-chloro-anthraquinones, for. example, 1-bromo-4-methoxyanthraquinone, 1-bromo-3-phenyloxy-4-aminoanthraquinone, l-amino-4-bromo-anthraquinone-2-carboxylic acid- N,N-dimethylamide, l-amino-4-chloro-2-methoxycarbonylanthraquinone, l-amino-4-bromo-2-m e thoxycarbonylanthraquinone, as well as anthraquinones that contain active halogen atoms, for example:

l-hydroxy-4-( 3-chlorocarbonylphenyl )-aminoanthraquinone and l-amino-2-bromo-4-( 3 -nitro-4'- chlorophenylsulphonyl)-amino--anthraquinone.

Another group of starting materials comprises the lnitro-anthraquinones which can be reacted with a styryl dyestuff containing a primary amino group by a method known per se, with replacement of the nitro group by the amino group, for example, 1,5-dihydroxy- 4,B-dinitro-anthraquinone. Moreover, there should be mentioned in this connection those a-hydroxyanthraquinones which in the presence of a reducing agent exchange hydroxyl groups for amino residues, especially 1,4-dihydroxyanthraquinone whose hydroxyl groups can be considered to be negative residues for the present purpose. r

Furthermore, there should be mentioned anthraquinone derivatives that contain in a-position one or several fibre-reactive groups, for example:

l-[4'(4"-chloro-6"-methoxy-l 5"-triazinyl-2"-amino)-anilino]-anthraquinone, 1 ,4-bis-(-y-chloro-B-hydroxy-propylamino anthraquinone, l-B-hydroxyethylamino-4-(-y-chloro-B-hydroxypropylamino)-anthraquinone, l-methylamino-4-(y-chloro-B-hydroxy-propyl)- amino-anthraquinone, l-(y-chloro-B-hydroxypropyl)-amino-4-(4'- methylcyclohexylamino)-anthraquinone, l -methylamino-4-[ 2 '-chloro-4'-bis-(hydroxyethyl)- amino-l ,3 ,5 -triazinylamino]-anthraquinone, l-methylamino-4-(2'-bromoethylamino)- anthraquinone, l,4-bis-(y-bromopropylamino)-anthraquinone, l -amin0-4-(3 -chloroacetyl-anilino )-anthraquinone, and the-dyestuffs of the formulae on t siengaaai H O IfH-CH:

and

CO If N-CHJ 'CHr-NHCOCH1C] NH CH3 acid 9 l Compounds belonging to the '2- or 3-phenyl- 0 z, R anthraquinones substituted in position 1,4,5,8 are the I I X following: Q

1,5-dihydroxy-4,8-diamino-2- or -3-(3'-methoxy-4'- i lN hydroxy-phenyl)-anthraquinone, 5 c l,5'dihydroxy-4,8-diamino-2- or -3-(4'-hydroxyi Z2 phenyl)-anthraquinone, 1,5-dihydroxy-4,8-diamino-2- or -3-(4'-hydroxy-2'- e y -p y q ne, in which 2,, 2,, Y, R,, c and X have the meanings d'e-- l,5dihydroxy-4,8-diamino-2- or -3-(4'-hydroxyfi d b phenyl)-6- or -7-bromo-anthraquinone and H. a v .UM 1,5-dihydroxy-4,8-diamino-2- 0r *3-(4'-hydroxy-3'- l-amino-Z-chlorocarbonyIA-nitroanthraquinone or 2'-bromophenyl)-anthraquinone.

It is preferable to start from anthraquinone derivatives that contain amino groups, advantageously only one amino group, as reactive group. 0

The reaction can be illustrated by the following typical reaction courses:

oo 00% CN OHCQNIMR:

N (111:!) Hm & cm

H: g N

s CH3 OzN 0 C=CH NRIR, ooocgti CN I on H 3 H gQ- i H 5 2 CH, N lreduction l-amino--bromo-anthraquinone 2-sulphonic acid chloride CO 0 C H O CO 111N J=CH Nana,

5N CN H;

N in which R, and R have the same meanings as above. in general, the reaction is carried out in an organic solvent, for example, tetrahydrofuran, dimethyl-glycol Q ether, dioxan chlorobenzene, nitrobenzene, dimethyl- 2 formamide or sulpholan, or man acid-binding organic H, N medium, for example, pyridine.

Acylation with fibre-reactive acylating agents The anthraquinoid dyestuffs containing at least one residue of a styryl dyestuff, prepared according to this invention, can subsequently be treated with a fibre- MmiMHmomarbomLimtmanthmduinone reactive acyla tmg agent provided they contain acylable groups, especially acylable ammo groups.

CH2 CN sired, anhydrides there are obtained dyestuffs which H I 5 are sparingly soluble or insoluble in water, whose mole- 5 2 7 cule contains at least one fibre-reactive group, for example, s-triazinyl residues, which carry on the triazine 1 1 2 ring 1 or 2 chlorineor bromine atoms, pyrimidyl resi- 0N dues which carry one or two chlorine atoms or one or 1, two arylsulphonyl or alkanesulphonyl groups on the py- 13m N rimidine ring, monoor bis-(y-halogeno-B- 'hydroxypropyU-amino groups, B-halogenethylsulphamyl residues, B-halogenethoxy groups, B-halogenethylmercapto groups, y-halogeno-B-hydroxypropylsulphamyl residues, chloroacetylamino groups, vinylsulpho- By the two last-mentioned reactions there are formed nyl groups, 2,3-epoxypropyl groups or other fibredyestuffs of the general formula reactive residues, preferably such as are free from By reaction with the corresponding halides or, if degroups imparting solubility in water.

(111) Use The dyestuffs described above contain no acid groups imparting solubility in water, especially no sulphonic acid groups, so that they are sparingly soluble to insoluble in water.

The water-insoluble dyestuffs, mixtures of such water-insoluble dyestuffs and their mixtures with other dye-stuffs are extremely suitable especially after having been finely dispersed, for example by grinding, pasting or precipitation for dyeing or printing synthetic fibres such, for example, as acrylic or acrylonitrile fibres, polyacrylonitrile fibres and copolymers of acrylonitrile and other vinyl compounds, for example, acrylic esters, acrylamides, vinylpyridine, vinylchloride or vinylidenechloride, copolymers of dicyanoethylene and vinylacetate, also acrylonitrile block copolymers, fibres of polyurethanes, polyolefins, cellulose triand Zl-acetate, polyamides, for example, nylon 6, nylon 6.6 or nylon 12, and more especially fibres of aromatic polyesters such as of terephthalic acid and ethyleneglycol or 1,4-dimethylolcyclohexane, and copolymers of terephthalic or isophthalic acid and ethyleneglycol.

Accordingly, the present invention also provides a process for dyeing or printing synthetic fibres, especially polyester fibres, wherein a dyestuff of anthraquinoid nature, which is free from sulphonic acid groups and contains at least one residue of a styryl dyestuff, a mixture of such a dyestuff, or a mixture of sucha dyestuff with another dyestuff, is used.

For dyeing, the water-insoluble dyestuffs are advantageously used in a finely dispersed form and dyeing is carried out in the presence of a dispersant, for example, sulphite cellulose waste liquor or of a synthetic detergent, or of a combination of different wetting and dispersing agents. As a rule, it is advantageous to convert the dyestuffs to be used in a dye preparation before dyeing, which preparation contains a dispersant and the finely dispersed dyestuff in such a form that when the dyestuff preparation is diluted with water a fine dispersion results. Such dyestuff preparations can be manufactured by a method known per se, for example by grinding the dry or wet dyestuff with or without addition of a dispersant during grinding. It is also possible to dye the afore-mentioned synthetic fibres in a solution of the dyestuff in an organic solvent.

In aiming at strong dyeings on polyethyleneterephthalate fibres it proved advantageous to add a swelling agent to the dyebath, or to carry out the dyeing process under super-atmospheric pressure at a temperature above 100 C, for example at 120 C. Suitable swelling agents are aromatic carboxylic acids, for example benzoic or salicylic acid, phenols, for example orthoor para-hydroxydiphenyl, salicylic acid methyl ester, aromatic halogen compounds, for example chlorobenzene, ortho-dichlorobenzene or trichlorobenzene, phenylmethylcarbinol or diphenyl. For dyeing under superatmospheric pressure it is advantageous to make the dyebath slightly acidic, for example by adding a weak acid, for example, acetic acid, to it.

The dyestuffs to be used acco rding to this invention are especially suitable for dyeing by the so-called thermosetting process according to which the fabric to be dyed is impregnated with an aqueous dispersion of the dyestuff, which advantageously contains 1 to 50 of urea and a thickener, especially sodium alginate, preferably at a temperature not exceeding 60 C and then to express it by a method known per se.

For fixing the dyestuff on it, the fabric thus impregnated, advantageously after first having been dried, for example in a current of warm air, is heated to a temperature above C, for example a temperature within the range from to 210 C.

The above-mentioned thermosetting process is especially suitable for dyeing union fabricas of polyester fibres and cellulose fibres, especially cotton. In this case the padding liquor contains, in addition to the unquaternated water-insoluble dyestuff to be used according to this invention, also dyestuffs suitable for dyeing cotton, or especially so-called reactive dyestuffs, that is to say dyestuffs that can be fixed on the cellulose fibre with formation ofa chemical bond, thus, for example, dyestuffs that contain a chlorotriazine or chlorodiazine residue. 1n the latter case it has been found advantageous to add an acid acceptor, for example, a carbonate, phosphate, borate or perborate of an alkali metal, or a mixture thereof, to the dyebath. When vat dyestuffs are used, the padded fabric is first heat-treated and then treated with an aqueous alkaline solution of one of the reducing agents conventionally used in vat dyeing.

The dyeing on polyester fibres obtained by the present process are advantageously subjected to an aftertreatment, for example, by heating them with an aqueous solution of a nonionic detergent.

The dyestuffs used in the present process may be applied by printing instead of by impregnation. For this purpose, for example, a printing ink is used that contains in addition to the auxiliaries generally used in printing for example, wetting and thickening agents, the finely dispersed dyestuff, if desired in admixture with one of the above-mentioned cotton dyestuffs, if desired in the presence of urea and/or of an acid acceptor.

Furthermore, it is also possible to dye or print in an organic liquor, for example in a mixture of perchloroethylene and sufficient dimethylacetamide to enable the dyestuff to dissolve in the dye liquor.

The new dyestuffs can also be used for spin-dyeing polyamides, polyesters or polyolefins. The polymer to be dyed is advantageously admixed with the dyestuff in the form of a powder, granules or chips, as a ready spinning solution or in the molten state, and the dyestuff is used in the dry state or in the form of a dispersion or solution in a solvent which, if desired, may be volatile.

The dyestuffs of the present invention can also be used for mass dyeing polymers of acrylonitrile, or polyolefins and other plastic masses, also for colouring oil paints and lacquers. If desired, the above-mentioned thermosetting process may be applied.

Some of the new dyestuffs are valuable pigments that can be used for a wide variety of pigment applications, for example in the finely dispersed form for dyeing rayon and viscose or cellulose ethers and esters, for the manufacture of inks, especially inks for ballpens, as well as for the manufacture of coloured lacquers or lake formers, solutions and products of acetylcellulose, nitrocellulose, natural or synthetic resins, for example, polymerization or condensation resins, for example aminoplasts, alkyd resins, phenoplasts, polyolefins, for example, polystyrene, polyvinylchlordie, polyethylene, polypropylene, polyvinylchloride, rubber, casein, silicone and silicone resins.

The following Examples illustrate the invention. Un-

is obtained; this dy'estuff dyes polyester fibres yellow shades. I I r U u 1 1.3 Parts of the 'd'yestuff of the formula (ll) and 40 parts of acetic anhydride are stirred for 2 hours in an oilbath mai ntained at 140 to 150C, then poured out oiier ice, the whole is left to stand for 1 hour and then suctioi -filtered, thoroughly washed with water and "dried, to give an almost quantitative yield of the dye- 'stu'ffof the formula I NH;

cmoo'ocim which dyes polyester fibres yellow shades.

. The catalytic hydrogenation of the 'dye'stuff of the formula (ill) in dime'thylfo rmamide in the presence of R an'eynickel give's, after't he calculatedquantity of hydr'o "en gas has been absorbed, an almost theoretical yield of the dyestuff of the formula which dyes polyester fibres vivid green shades having good fastness properties.

An analogous reaction produces the dyestuffs of the formula 3.3 Parts of lamino-4nitro-anthraquinone-Z- carboxylic acid chloride and 3.74 parts of a styryl dyestuff of the formula CH=C(CN);

in chlorobenzene are stirred for 16 hours on an oilbath maintained at C. The cooled reaction mixture is suctioned off, washed with chlorobenzene and then with methanol, and dried. 6 Parts of the resulting dyestuff of the formula (which dyespolyester fibres yellow shades) are catalyt-. ic'ally hydrogenated in 50 parts of dimethylformamide in the presence of Raney nickel, until the calculated quantity of hydrogen has been absorbed. The resulting dyestuffof the formula CII=C(CN)1 dyespolyester fibres green shades having good'fastness properties.

'In an analogous mariner there are obtained the dyestuffs of the formula up, to yield the dyestuff of the formula Manufacturing the styryl dyestuff 4 Parts of the product of the formula (prepared by acylating the B-hydroxyethyl compound with meta-nitrobenzoylchloride) in acetonitrile are hydrogenated with a catalyst of palladium on carbon until the quantity of hydrogen needed to reduce the nitro group has been absorbed. No more starting material can be identified in the thin-layer chromatogram. The acetonitrile is distilled off and the residue worked N C C2 5 i i I :0 H N i NC capo-00C The para-and ortho-aminobenzoyl esters are obtained in a similar manner. The styryl dyestuffs, in which the N-ethyl group is replaced by a substituted alkyl group, are obtained by using the suitably modified starting compounds.

EXAMPLE 3 5.65 Parts of the product of formula (II) mentioned in Example I and 2.26 parts-of chloroacetylchloride in nitrobenzene are stirred for hours at 90 to 95 C. After cooling, the batch is suction-filtered, washed with methanol and dried, to yield a product of the formula v 0 NH:

N CH=C(CN)1 CICH3COOH CH; 0 N01 which dyes polyester fibres yellow shades.

The catalytic hydrogenation of L9 parts of this product in parts of dimethylformamide with Raney nickel until the theoretical quantity of hydrogen gas has been absorbed gives an almost quantitative yield of a dyestuff of the formula OzN 0 EXAMPLE 4 3.5 Parts of l,5-dihydroxy 4,8-dinitroanthraquinone and 7.5 parts of a styryl dyestuff of the formula 0: O (ll H in nitrobenzene are stirred for 20 hours in a bath maintained at C with a catalytic quantity of copper-(l)- chloride. After cooling, the mixture is poured into methanol. The precipitated dyestuff is suctioned off and the filter cake boiled in methanol, suctioned off, washed with methanol and dried, to yield a dyestuff of the formula OH H OjN O i ii i R: 0 NH Q N CH 0-0-0111 IQ \CN When the product of the formula (II) mentioned in Example 1 is subjected to catalytic reduction with COOCzHa CN HOHiO, 0N

is obtained; it dyes polyester fibres brilliant green shades having excellent fastness properties.

.One Part of the resulting dyestuff is ground wet with two parts of anaqueous solution of 50 strength of the Y sodium salt of dinaphthylmethane-disulphonic acid and then dried.

This dyestuff preparation is stirred with 40 parts of an aqueous solution of 10 strength of the sodium salt of N-benzyl-u-heptadecyl-benzimiclazole-disulphonic acid and four parts of 40 acetic acid solution are added. This batch is diluted with water to form a dyebath of 4,000 parts. I

100 Parts of a cleaned polyester fibre fabric are immers ed in this dyebath at 50 C, the temperature is raised to 120 to l30 C during half an hour and dyeing is carried out in a closed vessel for 1 hour at this temperature. The material is then thoroughly rinsed. The

resulting brilliant green dyeing has excellent properties of fastness to light and sublimation.

EXAMPLE 6 When 33 parts of l-amino-4-nitro-anthraquinone-Z- carboxylic acid chloride are reacted with 13.5 parts of the styryl dyestuff of the formula (I) mentioned in Example 1, followed by catalytic reduction as described in Example 1, the dyestuff of the formula c NH, HIN b N H: H; C HgN v is obtained which also dyes polyester fibres fast green yl-cellulose (4 aqueous solution) and 700 parts of water by stirring the dyestuff preparation described above into the previously diluted thickening by means of a high-speed stirrer, and the mixture is then adjusted to a pl-I-value of 6 by means of acetic acid of 80 strength. A fabric of polyester fibres is padded in this liquor at 30 C and then expressed to a weight increase of' 60 and then dried at to C. The fabric is then heated on a tenter frame for 60 seconds at 210 C, then washed in hot water and thoroughly rinsed in cold water. A green dyeing of good fastness properties is obtained.

EXAMPLE 7 A mixture of 7.2 parts of l-amino-4- bromoanthraquinone-2-carboxylic acid chloride and 7.5 parts of the styryl dyestuff of the formula in 50 parts by volume of chlorobenzene is stirred and refluxed for 16 hours, then cooled and the residue is filtered off and washed with benzene. After drying, there are obtained 12.2 parts of the dyestuff of the formula which dyes polyester fibres strong, brilliant orange shades EXAMPLE 8 A mixture of 3.5 parts of l,5-dihydroxy-4,8-dinitroanthraquinone, 8 parts of the styryl dyestuff of the formula HzN-O-(f-NH-Cglit CN a) IL CQ and a catalytic quantity of copper-(l)-chloride in nitrobenzene is stirred for 24 hours on an oilbath at 180 C, then cooled, stirred into methanol and suctioned. The residue is boiled in methanol, filtered while warm,

washed with methanol and dried, to yield a green dyestuff of the formula NHGCONH-(Falia which on reduction with Raney nickel in dimethylformamide until the calculated quantity of hydrogen gas has been absorbed yields a green dyestuff of the formula NH: O OH E ii zm-Oconfl-c nm -hyde; condensation of the aldehyde with malodinitrile and reduction of the nitro group with hydrogen in the presence of Raney nickel in dimethylformamide.

We claimf I 1. An anthraquinoid dyestufi' which corresponds to the formula in which 2! is OH, NH, or NHR, where R is methyl or ethyl,

Z is N0 Br, NH or NHR where R is methyl or ethyl,

Z and Z are each, independently, N0 OH, NH or NHR where R is methyl or ethyl,

V is -O- or -NH-,

R is C -C alkylene,

R is unsubstituted C -C alkyl or C -C, alkyl substituted by cyano, chloro, C,-C,, alkoxy, hydroxy, C -C alkoxycarbonyl, C -C alkylcarbonyloxy, C C,- alkylcarbamoyloxy, phenylcarbamyloxy, C -C alkoxycarbonyloxy, phenyloxycarbonyloxy, cyanoethoxy, phenyl, chloracetogt'y, or benzoyloxy,

c and d are each, independently, H, Cl, CH C H OCH OC H phenylthio or phenoxy, and

X is carb(C -C )alkoxy, carbonamido, N-

methylcarbonamido, N,N-dimethylcarbonamido, phenylsulfonyl or cyano.

2. An anthraquinoid dyestuff as claimed in claim 1, wherein V is -O-, and c and d are each, independently, H, -CH -OCH or Cl.

3. An anthraquinoid dyestuff as claimed in claim 1 of the formula 4. An anthraquinoid dyestuff as claimed in claim fol the formula 5. An anthraquinoid dyestuff as claimed in claim 1 of the formula 

2. An anthraquinoid dyestuff as claimed in claim 1, wherein V is -O-, and c and d are each, independently, H, -CH3, -OCH3, or Cl.
 3. An anthraquinoid dyestuff as claimed in claim 1 of the formula
 4. An anthraquinoid dyestuff as claimed in claim 2 of the formula
 5. An anthraquinoid dyestuff as claimed in claim 1 of the formula 